Motor fuel additive composition

ABSTRACT

Disclosed is a leaded motor fuel additive composition which synergistically interacts with the alkyl lead additive to reduce both fuel intake system deposit formation and combustion chamber deposit formation, thereby reducing engine ORI and maintaining desired engine performance.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a leaded motor fuel additive composition forbulk fuel addition. More particularly, this invention relates to a motorfuel additive composition comprising: (a) a fuel conditioner componentcomprising (i) a polar oxygenated hydrocarbon compound, and (ii) anoxygenated compatibilizing agent; (b) an alkyl lead compound; and (c) alead scavenger compound for use in bulk production of motor fuelscontaining alkyl lead allowing lower levels of alkyl lead whileimproving performance and decreasing ORI.

Furthermore, this invention relates to a motor fuel additive compositioncomprising: (a) a detergent component selected from the group consistingof (i) a reaction product component which is the reaction product of asubstituted hydrocarbon and an amino compound, and (ii) a succinicanhydride or succinic dibasic acid and (iii) a polybutylamine orpolyisobutylamine; and (b) a fuel conditioner component comprising (i) apolar oxygenated hydrocarbon compound, and (ii) an oxygenatedcompatibilizing agent, (c) an alkyl lead compound; and (d) a leadscavenger compound, for use in bulk production of motor fuels containingalkyl lead allowing lower levels of alkyl lead while improvingperformance and decreasing ORI.

2. Description of the Related Art

The discovery of alkyl leads (tetra ethyl lead and tetra methyl lead) asoctane enhancers for gasoline, and the scavengers required to remove itfrom the engine were made by Thomas Midgley Jr. in 1922. The scavengers(ethylene dibromide and ethylene dichloride) function by providinghalogen atoms that react with the lead to form volatile lead halidesalts that can easily escape out through the vehicle exhaust.

In early years the use of lead additives to increase the octane ratingof gasoline enabled the development of modem high-compression gasolineengines. The alkyl leads rapidly become the most cost-effective methodof enhancing octane in gasoline. By 1970 almost all of the gasoline usedaround the world contained lead additives in many cases atconcentrations well above 0.4 grams per liter. The lead response of thegasoline (to increase the octane) decreases as the amount of lead isincreased. Typically at the 0.2 grams per liter level the octaneincrease is about 3 to 5 octane numbers. At the 0.4 grams per literlevel the octane increase is only about 5 to 7 octane numbers.Furthermore, the lead response of gasoline is greatly dependent upon thenature of the hydrocarbon streams in the gasoline. Thus to realizehigher octane number increases much larger amounts of lead would berequired.

Additionally, the use of lead in gasoline leads to emission of lead inthe form of very fine particles, which can be easily inhaled by humanbeings. Lead is known to contribute to high blood pressure, cancer, andheart disease in adults, and to reduced intelligence, behavioraldisorders, and impaired development in children, making the use of highlevels of lead in gasoline undesirable.

In addition, when alkyl leads are the sole octane enhancer in gasolinethe gasoline use in internal combustion engines increases maintenancecosts and reduces the life of the engines.

In view of the foregoing, it would clearly be advantageous to employ anadditive in alkyl lead containing motor fuel compositions which reducesdeposits in engine fuel intake systems and also avoids the formation ofdeposits in engine combustion chambers, thereby reducing or at leastmodifying the composition of deposits which tend to cause engine ORI.

It is an object of this invention to provide a motor fuel additive foralkyl lead containing motor fuels, which is useful in preventing bothfuel intake system deposit formation-and combustion chamber depositformation. It is a feature of this invention that the additive comprisesa detergent component and a fuel conditioner component, whichsynergistically interact to reduce both fuel intake system andcombustion chamber deposit formation. It is an advantage of thisinvention that it both reduces deposit formation in engine fuel intakesystems and ORI associated with combustion chamber deposit formation.

It is another object of this invention to provide a motor fuel additivewhich reduces deposits in engine fuel intake systems and also reducesthe amount of alkyl lead required in gasoline while maintaining engineperformance.

SUMMARY OF THE INVENTION

A leaded motor fuel additive composition which reduces and modifiescombustion chamber deposit formation for the purpose of reducing engineoctane requirement increase and allows the use of lower levels of alkyllead while retaining engine performance comprising a mixture of: (a) afuel conditioner component comprising: (i) from about 2 to about 50weight percent, based upon the total weight of the fuel conditionercomponent, of a polar oxygenated hydrocarbon having an average molecularweight in the range of about 200 to about 500, an acid number in therange of about 25 to about 175, and a saponification number in the rangeof about 30 to about 250, and (ii) from about 2 to about 50 weightpercent, based upon the total weight of the fuel conditioner component,of an oxygenated compatibilizing agent preferably having a solubilityparameter in the range of about 7.0 to about 14.0 and moderate to stronghydrogen-bonding capacity, (b) an alkyl lead compound; and (c) a leadscavenger compound.

Another object of the present invention is directed to a leaded motorfuel additive composition that reduces and modifies both fuel intakesystem and combustion chamber deposit formation for the purpose ofreducing engine octane requirement increase and allows the use of lowerlevels of alkyl lead while retaining engine performance comprising amixture of: (a) from about 5 to about 50 weight percent, based upon thetotal weight of components a and b, of a detergent component selectedfrom the group consisting of (i) a reaction product of: (A) asubstituted hydrocarbon of the formula

R₁—X   (I)

wherein R₁ is a hydrocarbyl radical having a molecular weight in therange of about 150 to about 10,000, and X is selected from the groupconsisting of halogens, succinic anhydride and succinic dibasic acid,and (B) an amino compound of the formula

H—(NH-(A)_(m))_(n)-Y—R₂   (II)

wherein Y is O or NR₅, R₅ being H or a hydrocarbyl radical having 1-30carbon atoms; A is a straight chain or branched chain alkylene radicalhaving 1-30 carbon atoms; m has a value in the range of 1-15; n has avalue in the range of 0-6; and R₂ is selected from the group consistingof H, a hydrocarbyl radical having a molecular weight in the range ofabout 15 to about 10,000, and a homopolymeric or heteropolymericpolyoxyalkylene radical of the formula

R₃-((Q)_(a)(T)_(b)(Z)_(c))_(d)-   (III)

wherein R₃ is H or a hydrocarbyl radical having 1-30 carbon atoms, Q, T,and Z are polyoxyalkylene moieties having 1-6 carbon atoms, a, b and ceach have values ranging from 0-30, and d has a value in the range of1-50, and (ii) a polybutylamine or polyisobutylamine of the formula

where R11 is a polybutyl or polyisobutyl radical derived from isobuteneand up to 20% by weight of n-butene and R12 and R13 are identical ordifferent and are each hydrogen, an aliphatic or aromatic hydrocarbon, aprimary or secondary, aromatic or aliphatic aminoalkylene radical orpolyaminoalkylene radical, a polyoxyalkylene radical or a heteroaryl orheterocyclyl radical, or, together with the nitrogen atom to which theyare bonded, form a ring in which further hetero atoms may be present;and (b) a fuel conditioner component comprising: (i) from about 2 toabout 50 weight percent, based upon the total weight of components a andb, of a polar oxygenated hydrocarbon having an average molecular weightin the range of about 200 to about 500, an acid number in the range ofabout 25 to about 175, and a saponification number in the range of about30 to about 250, and (ii) from about 2 to about 50 weight percent, basedupon the total of components a and b, of an oxygenated compatibilizingagent preferably having a solubility parameter in the range of about 7.0to about 14.0 and moderate to strong hydrogen-bonding capacity, (c)analkyl lead compound; and (d) a lead scavenger compound.

Yet another object of the present invention is directed to an additivecomposition for use in leaded motor fuel which reduces and modifies bothfuel intake system and combustion chamber deposit formation for thepurpose of reducing engine octane requirement increase and allows theuse of lower levels of alkyl lead while retaining engine performancecomprising a mixture of: (a) a fuel conditioner component having; (i)from about 2 to about 50 weight percent, based upon the total weight ofthe fuel conditioner component, of a polar oxygenated hydrocarbon havingan average molecular weight in the range of about 200 to about 500, anacid number in the range of about 25 to about 175, and a saponificationnumber in the range of about 30 to about 250; and (ii) from about 2 toabout 50 weight percent, based upon the total weight of the fuelconditioner component, of an oxygenated compatibilizing agent preferablyhaving a solubility parameter in the range of about 7.0 to about 14.0and moderate to strong hydrogen capacity; (b)an alkyl lead compound; (c)a lead scavenger compound; and (d) a detergent compound.

The fuel conditioner component may additionally comprise a hydrophilicseparant such as a glycol monoether. The additive composition mayadditionally comprise a carrier oil or fluidizer. This invention is alsodirected to a leaded motor fuel containing the present invention whichmay be added with the alkyl lead and any other additives or added afterthe addition of the alkyl lead and any other additives.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

This invention is in one aspect directed to a leaded motor fuel additivecomprising: (a) a detergent component which is selected from the groupconsisting of (i) the reaction product of a substituted hydrocarbon andan amino compound, (ii) a polybutylamine or polyisobutylamine; (b) afuel conditioner component comprising a polar oxygenated hydrocarboncompound and an oxygenated compatibilizing agent; (c) an alkyl leadcompound; and (d) a lead scavenger compound.

Another aspect of the present invention is directed to a leaded motorfuel additive comprising (a) a fuel conditioner component comprising apolar oxygenated hydrocarbon compound and an oxygenated compatibilizingagent; (b) an alkyl lead compound; and (c) a lead scavenger compound.

If the reaction product detergent component is employed, the substitutedhydrocarbon reactant used to prepare the reaction product is of theformula

R₁—X   (I)

wherein R₁ is a hydrocarbyl radical having a molecular weight in therange of about 150 to about 10,000, preferably a polyalkylene radicalhaving a molecular weight in the range of about 400 to about 5000, mostpreferably a polyalkylene radical having a molecular weight in the rangeof about 600 to about 1500, and X is selected from the group consistingof halogens, preferably chlorine, succinic anhydride and succinicdibasic acid. in one preferred embodiment, R₁—X is a polyisobutenylsuccinic anhydride. In another preferred embodiment, R₁—X is achloropolyisobutylene,

The amino compound reactant used to prepare the reaction product is ofthe formula

H—(NH-(A)_(m))_(n)-Y—R₂   (II)

wherein Y is O or NR₅, R₅ being H or a hydrocarbyl radical having 1-30carbon atoms, preferably 1-22 carbon atoms; A is a straight chain orbranched chain alkylene radical having 1-30, preferably 1-15 carbonatoms; m has a value in the range of 1-15, preferably 1-12; n has avalue in the range of 0-6, preferably 0-5; and R₂ is selected from thegroup consisting of H, a hydrocarbyl radical having a molecular weightin the range of about 15 to about 10,000, preferably 15 to about 2000,and a homopolymeric or heteropolymeric polyoxyalkylene radical of theformula

R₃-((Q)_(a)(T)_(b)(Z)_(c))_(d)-   (III)

wherein R₃ is H or a hydrocarbyl radical having 1-30, preferably 1-22carbon atoms, Q, T, and Z are polyoxyalkylene moieties having 1-6 carbonatoms, a, b, and c each have values ranging from 0-30, and d has a valuein the range of 1-50, preferably 1-25.

Various preferred embodiments of the amino compound reactant of formula(II) are given in Table 1 below:

TABLE 1 1. A = CH₂, m = 2, n = 3, Y = NR₅, R₅ = H, R₂ = H, yields anamino compound reactant of the formula:NH₂—(CH₂)₂—NH—(CH₂)₂—NH—(CH₂)₂—NH₂ 2. A = CH₂, m = 3, n = 1, Y = NR₅, R₅= H, R₂ = oleyl radical, yields an amino compound reactant of theformula: NH₂—(CH₂)₃—NH-oleyl 3. A = CH₂, m = 6, n = 1, Y = NR₅, R₅ = H,R₂ = H, yields an amino compound reactant of the formula: NH₂—(CH₂)₆—NH₂4. A = CH₂, m = 12, n = 1, Y = NR₅, R₅ = H, R₂ = H, yields an aminocompound reactant of the formula: NH₂—(CH₂)₁₂—NH₂

In another preferred embodiment, R₂ is the above-described homopolymericor heteropolymeric polyoxyalkylene radical of formula (III). As used inthis description and in the appended claims, the terms homopolymeric andheteropolymeric refer to polyoxyalkylene compounds, which in the case ofhomopolymeric compounds contain one recurring polyoxyalkylene moiety,and in the case of heteropolymeric compounds contain more than onerecurring polyoxyalkylene moiety, typically having 1-6 carbon atoms,such as ethylene oxide (EO), propylene oxide (PO) or butylene oxide(BO). Thus, for example, in one embodiment R₂ may be a homopolymericpolyoxyalkylene radical of the formula

R₃-((EO))_(d)-

wherein in formula (III), a=1, b=0, c=0, Q=ethylene oxide, and R₃ and dare as previously defined. In another embodiment, R₂ may be aheteropolymeric polyoxyalkylene radical of the formula

R₃-((EO)_(a)(PO)_(b)(BO)_(c))_(d)-

wherein, in formula III, Q=ethylene oxide, T=propylene oxide, Z=butyleneoxide, and a, b, c, d and R₃ are as previously described.

In yet another preferred embodiment, the above-described amino compoundreactant is selected from the group consisting of polyethylenepolyamines, polypropylene polyamines and mixtures thereof. In yetanother preferred embodiment, such polyamines are monoalkylated.

The reaction product component is preferably prepared by reacting thesubstituted hydrocarbon R₁—X to the amino compound in a mole ratio inthe range of 0.2:1-20:1, more preferably in the range of 0.5:1-10:1. Thereaction product component may be prepared under reaction conditions(including e.g. reaction times, temperatures, and reagent proportions)as are well known by those skilled in the art for preparing such aminocompound-substituted hydrocarbon reaction products. The method forpreparing such reaction products is described, for example, in U.S. Pat.No. 3,172,892 (LeSeur et al.), U.S. Pat. No. 3,438,757 (Honnen et al.),and U.S. Pat. No. 3,443,918 (Kautsky et al.), all of which areincorporated herein by reference.

The detergent compound may also be a polybutylamine or polyisobutylamineof the formula (IV)

where R11 is a polybutyl- or polyisobutyl radical derived from isobuteneand up to 20% by weight of n-butene, and R12 and R13 are identical ordifferent and are each hydrogen, an aliphatic or aromatic hydrocarbon, aprimary or secondary, aromatic or aliphatic aminoalkylene radical orpolyaminoalkylene radical, a polyoxyalkylene radical or a heteroaryl orheterocyclyl radical, or, together with the nitrogen atom to which theyare bonded, form a ring in which further hetero atoms may be present.

Compounds of the general formula (IV) and the method of preparationthereof are disclosed, for example, in U.S. Pat. No. 4,832,702 (Kummeret al.), incorporated herein by reference. Compounds of the generalformula (IV) are preferably prepared in accordance with the methoddisclosed in U.S. Pat. No. 4,832,702, wherein an appropriate polybuteneor polyisobutene is hydroformylated with a rhodium or cobalt catalyst inthe presence of CO and H2 at from about 80-200° C. and CO/H 2 pressuresof up to 600 bar, and the oxo product thereby formed is then subjectedto a Mannich reaction or amination under hydrogenating conditions,wherein the amination reaction is advantageously carried out at 80-200°C. and under pressures up to 600 bar, preferably 80-300 bar.

The fuel conditioner component employed in admixture with the detergentcomponent to produce the additive of this invention may preferably bethe fuel conditioner previously disclosed in U.S. Pat. No. 4,753,661(Nelson et al.), incorporated herein by reference. This fuel conditionercomprises a polar oxygenated hydrocarbon compound and an oxygenatedcompatibilizing agent.

The polar oxygenated hydrocarbon portion of the fuel conditionersignifies various organic mixtures arising from the controlled oxidationof petroleum liquids with air. Often these air oxidations of liquiddistillates are carried out at a temperature of from about 100° C. toabout 150° C. with an organo-metallic catalyst, such as esters ofmanganese, copper, iron, cobalt, nickel or tin, or organic catalysts,such as tertiary butyl peroxide. The result is a melange of polaroxygenated compounds which may be divided into at least threecategories: volatile, saponifiable and non-saponifiable.

The polar oxygenated compounds preferable for use in the presentinvention may be characterized in a least three ways, by molecularweight, acid number, and saponification number. It is to be appreciatedby those skilled in the art that the terms “molecular weight” and“average molecular weight” are synonymous and are herein usedinterchangeably. It is to be further appreciated that there are severalmethods of determining the average molecular weight of an organicmaterial and that different methods will produce different results forthe same material. Chemically these oxidation products are mixtures ofacids, hydroxy acids, lactones, eaters, ketones, alcohols, anhydrides,and other oxygenated organic compounds. Those suitable for the presentinvention are compounds and mixtures with an average molecular weightbetween about 200 and about 500, with an acid number between about 25and about 175 (ASTM-D-974), and a saponification number from about 30 toabout 250 (ASTM-D-974-52). Preferably the polar oxygenated compounds ofthe present invention have an acid number from about 50 to about 100 anda saponification number from about 75 to about 200.

Suitable compatibilizing agents for use in the fuel conditionercomponent of the instant invention are organic compounds of moderatesolubility parameter and moderate to strong hydrogen-bonding capacity.Solubility parameters, based on cohesive energy density are afundamental descriptor of an organic solvent giving a measure of itspolarity. Simple aliphatic molecules of low polarity have a low . ofabout 7.3; highly polar water has a high . of 23.4. Solubilityparameters, however, are just a first approximation to the polarity ofan organic solvent. Also important to generalized polarity, and hencesolvent power, are dipole moment and hydrogen-bonding capacity.Symmetrical carbon tetrachloride and some aromatics with low grossdipole moment and poor hydrogen-bonding capacity have a solubilityparameter of about 8.5. In contrast, methyl propyl ketone has almost thesame solubility parameter, 8.7, but quite strong hydrogen-bondingcapacity and a definite dipole moment. Thus, no one figure of meritalone describes the “polarity” of an organic solvent.

For the practice of the present invention a compatibilizing agentpreferably having a solubility parameter from about 7.0 to about 14.0and moderate to strong hydrogen-bonding capacity. Suitable classes oforganic solvents are alcohols, ketones, esters, and ethers. The fuelconditioner component of this invention may additionally include ahydrophilic separant which decreases the amount of water in thehydrocarbon fuel, thus improving combustion. Suitable separants forpracticing the current invention are ethers of glycols or polyglycols,especially monoethers. Monoethers are preferred over diethers in thepractice of the present invention.

Examples of such compounds which may be used are the monoethers ofethylene glycol, propylene glycol, trimethylene glycol, alphabutyleneglycol, 1,3-butanediol, beta-butylene glycol, isobutylene glycol,tetramethylene glycol, hexylene glycol, diethylene glycol, dipropyleneglycol, tripropylene glycol, triethylene glycol, tetraethylene glycol,1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol,2-ethyl-1,3-hexanediol. Some monoethers include ethylene glycolmonophenyl ether, ethylene glycol monomethylether, ethylene glycolmonoethyl ether, ethylene glycol mono-(n-butyl) ether, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycolmono-(n-butyl) ether, propylene glycol monomethyl ether, dipropyleneglycol monomethyl ether, diethylene glycol monocyclohexylether, ethyleneglycol monobenzyl ether, triethylene glycol monophenethyl ether,butylene glycol mono-(p-(n-butoxy) phenyl) ether, trimethylene glycolmono(alkylphenyl) ether, tripropylene glycol monomethyl ether, ethyleneglycol mono-isopropyl ether, ethylene glycol monoisobutyl ether,ethylene glycol monohexyl ether, triethylene glycol monobutyl ether,triethylene glycol monomethyl ether, triethylene glycol monoethyl ether,1-butoxyethoxy-2-propanol, monophenyl ether of polypropylene glycolhaving an average molecular weight of about 975 to 1075, and monophenylether of polypropylene glycol wherein the polyglycol has a averagemolecular weight of about 400 to 450, monophenyl ether of polypropyleneglycol wherein the polypropylene glycol has an average molecular weightof about 975 to 1075. Such compounds are sold commercially under tradenames such as Butyl CELLOSOLVE, Ethyl CELLOSOLVE, Hexyl CELLOSOLVE,Methyl CARBITOL, Butyl CARBITOL, DOWANOL Glycol ethers, and the like.

The composition of this invention may additionally comprise a suitableamount of a carrier oil or fluidizer selected from the group consistingof petroleum-based oils, mineral oils, polypropylene compounds having amolecular weight in the range of about 500 to about 3000,polyisobutylene compounds having a molecular weight in the range ofabout 500 to about 3000, polyoxyalkylene compounds having a molecularweight in the range of about 500 to about 3000, and polybutyl andpolyisobutyl alcohols containing polybutyl or polyisobutyl radicalsderived from polyisobutene and up to 20% by weight of n-butene,corresponding carboxylates of the polybutyl or polyisobutyl alcohol, andmixtures thereof. Petroleum based oils which may be employed include topcylinder oils as well as both natural and synthetic naphthenic andparaffinic base stock oils of relatively high viscosity, includingso-called Solvent Neutral Oils (SNO) such as SNO-500 and SNO-600.Mineral oils which may be employed include so-called “light” mineraloils, i.e. those petroleum, aliphatic or alicyclic fractions having aviscosity less than about 10,000 SUS at 250° C. A mixture of hydrocarbonfractions may also be employed in place of a base stock. Theabove-described polybutyl and polyisobutyl alcohols include thosedisclosed in U.S. Pat. No. 4,859,210 (Franz et al.), incorporated hereinby reference. As used in this description and in the appended claims,the terms “carrier oil” and “fluidizer” are interchangeable, as will bereadily understood by those skilled in the art.

TABLE 2 Given the presence of the many constituents described above, aUseful Range Preferred Range Detergent Component 5-50 10-40  PolarOxygenated Compound 2-50 10-40  Compatibilizing Agent 2-50 5-25Hydrophilic Separant 0-40 0-30 Carrier Oil 0-40 0-30 Alkyl LeadCompounds 5-50 20-40 

Suitable alkyl lead compounds for use in the present invention includefor example, tetra ethyl lead and tetra methyl lead. Preferably theamount of alkyl lead compounds is less than 0.4 grams per liter and mostpreferably less than 0.2 gramps per liter.

Suitable lead scavengers for use in the present invention, include forexample, ethylene dibromide and ethylene dichloride.

The additive composition of this invention may be employed in a widevariety of hydrocarbon or modified hydrocarbon (e.g. alcohol-containing)fuels for a variety of engines. Preferred motor fuel compositions foruse with the additive composition of this invention are those intendedfor use in spark ignition internal combustion engines. Such motor fuelcompositions, comprise a fuel component generally referred to asgasoline base stocks, preferably comprise a mixture of hydrocarbonsboiling in the gasoline boiling range, preferably form about 90-450° F.This base fuel may consist of straight chains, branch chains, paraffins,cycloparaffins, olefins, aromatic hydrocarbons, and mixtures thereof.The base fuel may be derived from, among others, straight run naphtha,polymer gasoline, natural gasoline, or from catalytically cracked orthermally cracked hydrocarbons and catalytically reformed stock. Thecomposition and octane level of the base fuel are not critical and anyconventional leaded motor base fuel may be employed in the practice ofthis invention. In addition, the motor fuel composition may additionallycomprise other additives typically employed in motor fuels, such asanti-icing additives, upper cylinder lubricating oils, carburetordetergents, anti-corrosion additives, de-emulsifying agents, odorsuppressors, and the like.

Throughout the specification, examples and claims the followingdefinitions are used.Combustion Chamber Deposits (CCD) means deposits formed in thecombustion chamber of an engine, due to the deposition of carbonaceousdeposits of unburned fuel components and deposits from other additivespresent in the fuel.

Octane Requirement Increase (ORI) means the increase in octanerequirement that results from the buildup of combustion chamberdeposits. ORI begins to build up as soon as a new engine is started forthe first time as CCDs begin to form in the combustion chamber of theengine. ORI reaches equilibrium between 10,000 to 15,000 miles in thelife of a new engine. The octane requirement increase is typically 5-8octane numbers by the time equilibrium is reached.

Octane Number Required (ONR) means the octane level required to provideknock-free operations in a given engine.

Octane Enhancer means components that are added to gasoline to increaseoctane and to reduce engine knock, such as for example, alkyl lead.

Valve Seat Recession (VSR) means the phenomenon in which the exhaustvalve seat experiences wear and the valve seat recesses further into thesurface of the engine head. Excessive valve seat recession can result inengine failure. Lead in gasoline provides a coating to this surface andprevents valve seat recession.

Having described this invention above, it is now illustrated in thefollowing example. This example, however, does not limit the applicationof this invention, which may be carried out by other means in othersystems.

EXAMPLE 1

The following experiment shows the leaded fuel additive of the presentinvention to reduce both ORI and Knock Limited Spark Advance (KLSA).This bench test used a Renault 25 GTX Engine running on a commerciallyavailable leaded motor fuel and a fuel containing the invention for 100hours. The results are summarized below:

Engine RPM Leaded Fuel ORI (at 100 hours) 500 ppm invention additivewithout detergent 2500 4.1 1.9 (reduction of 2.2) 3500 4.0 1.5(reduction of 2.5) ΔKLSA* (at 100 hours) 100 ppm invention additive witha detergent Leaded Fuel package 2000 7.6 1.9 (reduction of 5.7) 2900 8.04.0 (reduction of 4.0) 3600 9.25 2.75 (reduction of 6.5)  4100 8.0 3.5(reduction of 4.5) *2 KLSA numbers = 1 Research Octane Number

Thus in leaded gasoline, the alkyl lead raises the octane number of thegasoline by a few points while the additive of the present inventionreduces the ONR and maintains combustion chamber cleanliness. Thiscombination of alkyl lead in the present invention additive in thegasoline functions as if the octane has been raised to a much higherlevel than the measured octane number improvement by the alkyl leadadded alone. This combination enhances vehicle performance, improvesfuel economy, and reduces CO and HC emissions. In addition, the use ofthe present invention additive with alkyl lead allows the use of a loweralkyl lead amount while retaining the same overall octane efficiencybenefits to the engine.

EXAMPLE 2

The following experiment shows the leaded fuel additive of the presentinvention to reduce both ORI and intake valve deposits in fuels. SeveralRenault and Peugeot cars some carbureted and some injected were run for10,000 km (6,250 miles) and the ORI of the engines measured before andafter the tests. The ORI was reduced by up to 80% in engines using fuelcontaining the invention over engines using commercially availableleaded fuels. Additionally, inlet valve deposits were reduced by up to90% using fuel containing the invention over engines using commerciallyavailable leaded fuels.

1. An additive composition for use in leaded motor fuel which reducesand modifies both fuel intake system and combustion chamber depositformation for the purpose of reducing engine octane requirement increaseand allows the use of lower levels of alkyl lead while retaining engineperformance comprising a mixture of: (a) a fuel conditioner componenthaving; (i) from about 2 to about 50 weight percent, based upon thetotal weight of the fuel conditioner component, of a polar oxygenatedhydrocarbon having an average molecular weight in the range of about 200to about 500, an acid number in the range of about 25 to about 175, anda saponification number in the range of about 30 to about 250; and (ii)from about 2 to about 50 weight percent, based upon the total weight ofthe fuel conditioner component, of an oxygenated compatibilizing agentpreferably having a solubility parameter in the range of about 7.0 toabout 14.0 and moderate to strong hydrogen capacity; (b)an alkyl leadcompound; and (c) a lead scavenger compound.
 2. The leaded motor fueladditive composition according to claim 1, allowing the alkyl lead to bereduced below 0.4 grams per liter while maintaining desired engineperformance.
 3. The leaded motor fuel additive composition according toclaim 1, allowing the alkyl lead to be reduced below 0.2 grams per literwhile maintaining desired engine performance.
 4. The leaded motor fueladditive composition according to claim 1, wherein said additivecomposition is used in an amount of from about 100 ppm to about 1000ppm.
 5. An additive composition for use in leaded motor fuel whichreduces and modifies both fuel intake system and combustion chamberdeposit formation for the purpose of reducing engine octane requirementincrease and allows the use of lower levels of alkyl lead whileretaining engine performance comprising a mixture of: (a) a fuelconditioner component having; (i) from about 2 to about 50 weightpercent, based upon the total weight of the fuel conditioner component,of a polar oxygenated hydrocarbon having an average molecular weight inthe range of about 200 to about 500, an acid number in the range ofabout 25 to about 175, and a saponification number in the range of about30 to about 250; and (ii) from about 2 to about 50 weight percent, basedupon the total weight of the fuel conditioner component, of anoxygenated compatibilizing agent preferably having a solubilityparameter in the range of about 7.0 to about 14.0 and moderate to stronghydrogen capacity; (b)an alkyl lead compound; (c) a lead scavengercompound; and (d) a detergent compound.
 6. The leaded motor fueladditive composition according to claim 5, wherein said additivecomposition is used in an amount of from about 100 ppm to about 500 ppm.7. The leaded motor fuel additive composition according to claim 1,wherein said additive composition is added to the leaded motor fuelsimultaneously with any other additives.
 8. The leaded motor fueladditive composition according to claim 1, wherein said additivecomposition is added to the leaded motor fuel after any other additiveshave been added.
 9. The leaded motor fuel additive composition accordingto claim 1, wherein said alkyl lead compound is selected from the groupconsisting essentially of tetraethyl lead and tetramethyl lead.
 10. Theleaded motor fuel additive composition according to claim 1, whereinsaid alkyl lead compound is present in an amount of from about 0.05 toabout 0.5 grams per liter.
 11. The leaded motor fuel additivecomposition according to claim 1, where said lead scavenger compound isselected from the group consisting essentially of ethylene dibromide andethylene dichloride.
 12. A leaded motor fuel additive composition whichreduces and modifies both fuel intake system and combustion chamberdeposit formation for the purpose of reducing engine octane requirementincrease and allows the use of lower levels of alkyl lead whileretaining engine performance comprising a mixture of: (a) from about 5to about 50 weight percent, based upon the total weight of components aand b, of a detergent component selected from the group consisting of(i) a reaction product of: (A) a substituted hydrocarbon of the formulaR₁—X   (I) wherein R₁ is a hydrocarbyl radical having a molecular weightin the range of about 150 to about 10,000, and X is selected from thegroup consisting of halogens, succinic anhydride and succinic dibasicacid, and(B)an amino compound of the formulaH—(NH-(A)_(m))_(n))-Y—R₂   (II) wherein Y is O or NR₅, R₅ being H or ahydrocarbyl radical having 1-30 carbon atoms; A is a straight chain orbranched chain alkylene radical having 1-30 carbon atoms; A isstraight-chain or a branched-chain alkylene radical having 1-30 carbonatoms, m has a value in the range of 1-15; n has a value in the range of0-6; and R₂ is selected from the group consisting of H, a hydrocarbylradical having a molecular weight in the range of about 15 to about10,000, and a homopolymeric or heteropolymeric polyoxyalkylene radicalof the formulaR₃-((Q)_(a)(T)_(b)(Z)_(c))_(d)-   (III) wherein R₃ is H or a hydrocarbylradical having 1-30 carbon atoms, Q, T, and Z are polyoxyalkylenemoieties having 1-6 carbon atoms, a, b and c each have values rangingfrom 0-30, and d has a value in the range of 1-50, and (ii) apolybutylamine or polyisobutylamine of the formula

where R₁₁ is a polybutyl or polyisobutyl radical derived from isobuteneand up to 20% by weight of n-butene and R₁₂ and R₁₃ are identical ordifferent and are each hydrogen, an aliphatic or aromatic hydrocarbon, aprimary or secondary, aromatic or aliphatic aminoalkylene radical orpolyaminoalkylene radical, a polyoxyalkylene radical or a heteroaryl orheterocyclyl radical, or, together with the nitrogen atom to which theyare bonded, form a ring in which further hetero atoms may be present;(b) a fuel conditioner component comprising: (i) from about 2 to about50 weight percent, based upon the total weight components a and b, of apolar oxygenated hydrocarbon having an average molecular weight in therange of about 200 to about 500, an acid number in the range of about 25to about 175, and a saponification number in the range of about 30 toabout 250, and (ii) from about 2 to about 50 weight percent, based uponthe total of components a and b, of an oxygenated compatibilizing agentpreferably having a solubility parameter in the range of about 7.0 toabout 14.0 and moderate to strong hydrogen capacity; (c) an alkyl leadcompound; and (d) a lead scavenger compound.
 13. The leaded motor fueladditive composition according to claim 12, wherein said alkyl leadcompound is selected from the group consisting essentially of tetraethyllead and tetramethyl lead.
 14. The leaded motor fuel additivecomposition according to claim 12, wherein said alkyl lead compound ispresent in an amount of from about 0.05 to about 0.5 grams per liter.15. The leaded motor fuel additive composition according to claim 12,where said lead scavenger compound is selected from the group consistingessentially of ethylene dibromide and ethylene dichloride.
 16. Theleaded motor fuel additive composition according to claim 12, allowingthe alkyl lead to be reduced below 0.4 grams per liter while maintainingdesired engine performance.
 17. The leaded motor fuel additivecomposition according to claim 12, allowing the alkyl lead to be reducedbelow 0.2 grams per liter while maintaining desired engine performance.18. The leaded motor fuel additive composition according to claim 12,wherein said additive composition is used in an amount of from about 100ppm to about 1000 ppm.